Silver halide emulsion containing n-(alkylsulfonylphenyl)-1-hydroxy-2-naphthoic acid amide color couplers



1963 R. K. VAN POUCKE ETAL 3,0

SILVER HALIDE EMULSION CONTAINING N- ALKYLSULFONYLPHENYL -l-HYDROXY Z-NAPHTHOIC ACID 'AMIDE COLOR COUPLERS Filed Nov. 5. 1960 w k; N Q Q N v I i I l l a a; Q M Q INVENTORS zzfzfiazae z/xze mi AZ/X Vrfiflggykfi, BY

mmfiwwb Mu ATTORNEYS United States Patent 3,079,256 SILVER HALIDE EMULSHQN CQNTAINING N-(AL- KYLSULFONYLPHENYL) l-HYDRQXY-Z-NAiH- THiriC ACE) AMEDE CQLOR CGUPLERS Raphael Karel Van Pouelre, Mechiin, Arthur Henri De Cat, Mortsei-Antwerp, and Marcel Hendrik Verbrugghe, t'VilriiinAntwerp, Beigium, assignors to Gevaert Photo-Predation N.V., Mortsel-Antwerp, Belgium, 21 Beigian company Filed Nov. 3, Haiti, er. No. 66,964 Claims priority. a plication Belgium Nov. 2%, 1959 Claims. (81. 96-55) The present invention relates to a process for the manufacture of photographic color images and also to color correction.

it is known that a colored image may be formed by incorporating into the silver halide emulsion a compound which couples during development with the oxidation product of the developing agent and forms a colored compound in the same area where the silver halide grains are reduced.

Such a compound which is employed in conjunction with the developing agent for the silver and which conpics with the oxidation product of the developing agent during development is referred to herein as a colorforming compound or coupler.

The modern processes of color photography are based upon the subtractive color principle according to which differently sensitized silver halide emulsions are superposed in the form of layers. Each of these layers contains the different color forming compounds which produce on development the subtractive yelloW-cyanand magenta-color images. The usual developing substance is a primary aromatic amine.

The dyestuffs and pigments used in practice in subtractive processes of color photography do not possess ideal spectral absorption curves. in addition to absorbing light in the desired part of the spectrum, they also absorb some light in other parts of the spectrum and, as a result thereof, the color reproduction is never ideal. For example, cyan dyestuifs formed by color development from color formers oi the l-naphthol series absorb the desired complementary colored red-light and in addition absorb undesirably a certain amount of blue and green light.

It has been proposed to correct for these deficiencies by the use of an automatic masking method, whereby after the usual color development and treatment in a bleaching bath the unchanged color former reacts with the oxidation product of a 4-amino-3-pyrazolone derivative to form a magenta dyestuif so that it absorbs blue and green light at an intensity equal to the undesired blue and green absorption of the cyan dyestuif formed by color development. This process of masking is described in the US. application Serial No. 705,508, filed December 27, 1957.

It is known that different demands are made upon the color couplers according to whether they are designed for negative or for positive material. E.g. it is known that l-hydroxy-Z-naphthamide color couplers, giving after color development pure blue images, are preferably used for the manufacture of positive color materials. On the other hand it is preferable for the manufacture of negative materials to use l-hydroxy-Z-naphthamide color couplers producing a cyan image, and the absorption spectrum of which is shifted as far as possible to the longer wave-lengths showing thereby side-absorptions which are as low as possible. But the disadvantage of the batho chromic shifting of the absorption spectrum is that this action in most cases is accompanied by an increase of 3,@?9,25h Patented Feb. 26, 19%3 colored images with increased transparency in the green by using l-hydroxy-Z-naphthoic acid anilide color couplers which correspond to the general formula:

X is a member selected from the group consisting of a hydrogen atom, a halogen atom, a sulphonic acid group or a sulphonate group;

Y is a member selected from the group consisting of a hydrogen atom, a carboxyl group, a suiphonic acid group or a sulphonate group,

R represents a radical comprising a linear chain of at least 5 and at most 20 C-atoms making the molecule non-migratory in the emulsion layer.

Comparative absorption curves are given hereinafter which elucidate the favorable absorption spectrum and particularly the increased transparency in the green of the dyestuff images obtained with these color couplers.

An advantage of the color couplers according to the present invention with regards to the above-mentioned US. application Serial No. 705,508, filed December 27, 1957, and to the German patent application 6 30,580 consists therein that they form a mask dyestufi image since they easily react in an oxidative medium with 4- arninopyrazolone-3 and derivatives thereof with the following general formula:

R is a lower alkyl group, e.g. a methyl group;

R represents a lower alkyl group, e.g. a methyl group or an aryl group, such as a phenyl group or a substituted phenyl group;

R represents an aliphatic radical making the molecule non-migratory with more than 5 and less than 20 carbon atoms e.g. consisting of a nonyl, an undecyl, a tridecyl or a pentadecyl group.

Examples of such 4-aminopyrazolone-3 are among others:

1,2-dimethyl-4-amino-5-nonylpyrazolone-3 3 1,2-dimethyl-4-amino-5-undecylpyrazolone-3 1,2-dirnethyl-4-amino-5-tridecylpyrazolone-3 1,Z-dirnethyl-4-amino-5-pentadecylpyrazolone-3 1-rnethyl-2-(p-carbethoxyphenyl)-4-amino pentadecyl pyrazolone-3 V Methylester of 1-methyl-2 (p-succinylamidophenyl) -4- amino-5 pentadecylpyrazolone 1-methyl-2-(2' chloro 5-carbomethoxyphenyl)-4 amino- 5-pentadecylpyrazolone-3.

The preparation and the use of these compounds is described in the German patent application G 30,580. In this way, the application of the present invention may be possible'not only to compensate the remaining low side-absorption in the green but also almost completely the side-absorption in the blue, so that finally a cyan irjnage is obtained the absorption of which is almost 1 ea The new color couplers can be prepared by condensation of a l-hydroxy-Z-naphthoic acid or a derivative thereof with desired aromatic amines. In order to prepare color couplers which contain in their naphthol or anilide group a sulphonic acid group it is advantageous before the condensation to introduce a sulfo-fluoride group into the naphthol resp. anilide group which after condens a-, tion is saponified to the corresponding sulphonic acid, e.'g. by application of the process described in the Belgian Patents 584,152 and 590,934.

The preparation of such new color couplers is described hereinafter by way of example.

1. Preparation of N-(3-carboxy-4'-cctylphonylphenyl)- I-kydroxy-Z-rmphthoic acid amide. g. of 2-chloro-5- nitrobenzoic acid (Hubner: Ann. 222, 195) are dissolved in 100 cm. of methyl Cellosolve to which 5.6 g. of potassium hydroxide were added. A second solution is obtained by dissolving inSOcrn. of methyl Cellosolve, 25.8 g. of cetyl mercaptane together with 5.6 g. of potassium hydroxide. Both solutions are mixed and refluxed for 1 hour. The potassium chloride obtained is filtrated' 0d, the mixturestill being warm. After acidifying with acetic acid and after diluting with 500 cm? of methanol a precipitate is obtained which is recrystallized from methanol.

4 (NS) 10 part 5, Sect. A, pp. 131-134) and 13.64 g. of o-cetylsulphonylaniline are before thoroughly mixing heated to 170 C. on an oihbath. The phenol is distilled off under a reduced pressure of :8 mm. After 2 hours the heated reaction mixture is poured out into methanol. After recrystallization from a mixture of benzene and hexane a granular product is obtained. Melt- The obtained 2-cetyl-rnercaptof5-nitro" benzoic acid has a melting point of 108 C. 42.3 g. of this 2-cetylmercapto-S-nitrobenzoic acid are refluxed'together with 150 cm. of acetic acid. A dark brown solution is obtained to which 70 cm. of a hydrogen peroxide solution 30% in water are dropwise added whilst stirring (exothermic reaction); refluxing is continued for 1 hour. After cooling a white amorphous product is obtained which is recrystallized from acetic acid giving thereby the 2-cetyl sulphonyl-5-nitrooenzoic acid. Melting point: 97 C.

45.5 g. of this nitrobenzoic acid derivatives which are dissolvedin 3 00 cm. of ethanol are introduced into a hydrogenation autoclave under addition. of. Raney nickel. Hydrogen is introduced till a pressure of 70 kg./cm. is

reached. The temperatureis brought at 55 C. Within the course of 3 /2 hours of shaking the theoretically determined quantityo'f hydrogen is absorbed. The Raney nickel is filtrated 0d andthe filtrate is evaporated to dryness. After recrystallization from a mixture of acetic acid and water a 2-cetylsulphonyl-S-aminobenzoic acid is obtained under the form of a white crystalline product. Melting point: 119C.

12.75 g. of thisarnino. derivative and 7.92 g. of hydroxynaphthoic acid phenyl ester are melted together. The phenol 'is distilled off under reduced pressure varying between 2 and 5 mm. Hg. The product is poured out into methanol and. recrystallized from acetonitrile. White crystals of N-(3'-carboxy-4'-cetylsulphonylphenyb-lrhydroxy 2-naphthoic acid amide are formed in this way. Melting p'oint 146 C. i

II. Preparation of N-(o-cetylsulpkonylphenyl)J kydroxy-4-chloro-2-nzzgihthoicKqcid amide.-10.65 g. of 1- hydroxy-4-chloro-2-phenyl naphthoate (I. Univ. Bombay ing ponit: 102 C.

III. The preparation of N-(6'-cetylsulphonylphenyl)-lhydroxy-Z-n-aphthoic acid amide-3-sodium sulphonate is described in the German patent application G 30,287 (preparation 13).

IV. Preparation of N-(6'-cetylsulphonylphenyl)-1-hydroxy-4-chloro-2-naphthcic acid ami-de-3'-sodium sulphonate is described in German patent application G 30,287 (preparation 15).

V. Preparation of N-(6'-cetylsulphonylphenyl)-1-hydroxy-Z-naphthoic acid amide-3'-4-disodium sulphonate is described in the German patent application G 30,287 (preparation 16) V-I. Preparation of N-(4'-cetylsulphonylphenyl)-l-hydroXy-Z-naphthoic acid amide-3-sodium sulphonate is described in the German patent application G 30,287 (preparation 14).

VII. The preparation of N-(o-cetylsulphonylphenyl)- l-hydroxy-2-naph'thoic acid amide-4-sodium sulphonate is described in Belgian patent specification 584,152-Tab1e 11, Example 5.

For carrying out the process according to the present invention, the color couplers and mask compounds must be incorporated into a photographic silver halide emulsion prepared by means of the usual colloids, such as for instance gelatin, polyvinyl alcohol, collodion or other natural or synthetic colloids and such as for instance those of the Belgian Patent 568,153. The silver halide emulsioncan be coated on a support consisting of paper, glass,- nitrocellulose, cellulose esters such as cellulose triacetate, polyester, polystyrene or another natural of synthetic resin, and form part of a photographic material with one or more emulsion layers. The multilayer material is usually composed of the following sequence of layers: a support, an emulsion layer sensitized to red having a color coupler for cyan, an emulsion layer sensitized to green having a color coupler for magenta and an emulsion layer sensitive to blue having a color coupler for yellow. There is a yellow filter composed in most of the cases of colloidal silver, located between the blue-sensitive and the emulsion layer sensitized to green.

It is not only possible to incorporate the new color couplers into the light-sensitive silver halide emulsion layer itself but they can also be incorporated into an adjacent non-light-sensitive colloid layer or into a non-lightsensitiye layer which is separated from the light-sensitive emulsion layer by a water-permeable colloid layer.

The following aromatic amino-compounds can be used as developers for such material: mono, diand triaminoar yl compounds, more specifically. N,N-di alkyl-p-phenylenediamine and its derivatives such as N,N dialkyl-N sul'phomethylor carboxy-rnethyl p-phenylene diamine. As useful monoamiuo-developers should be cited: aminophenols and "amino cresols or their halogen derivatives andalso the aminonaphthols.

The following examples illustrate the present invention without limiting, however, the scope thereof. We draw the attention to the fact that all the quantities mentioned hereafter. are parts by weight when no other indication is given.

EXAMPLE 1 10 parts of 'N- (4'-cetyl-sulphonylphenyl) -1-hydroxy-2- naphthoic acid amide-3'-sodium sulphonate are wetted' by 40 parts of ethanol and brought intosolution by heating at40 C. by means of-2O parts of water. This solution is diluted with water up to 200parts whereby a solution 5%; is obtained. 200 parts of this color coupler solution together with 260 parts of water are added to 500 parts.

Sodium sulphite 2 Potassium carbonate 75 Potassium bromide 0.5 I-lydroxylamine hydrochloride 1.2 Sodium hexametaphosphate 1.0

Water to 1000 cm.

This material is rinsed for 30 seconds and fixed in an acid fixing bath of the following composition:

G. Sodium thiosulphate (dry) 200 Borax 8 Sodium sulphite 25 Potassium alum 15 Boric acid 7.5

Water to 1000 cm.

Now the material is rinsed for 10 min. and bleached in a bath of the following composition:

G. Potassium ferricyanide 100 Potassium bromide 25 Borax 20 Boric acid Water to 1000 cm.

Finally the material is rinsed for 5 min. and fixed in a bath of the following composition:

. G. Sodium thiosulphate (dry) 130 Sodium sulphite Sodium carbonate- 14 Water to 1000 cm.

An intense cyan image showing very low side-absorptions in the green spectrum is obtained.

EXAMPLE 2 10 parts of N-(6'-cetylsulphonylphenyl)-1-hydroxy-2- naphthoic acid amide-4,3'-disodium sulphcnate are Wetted with parts of ethanol and dissolved in 180 parts of water. The color coupler solution is incorporated into the emulsion according to the method described in Example 1. After exposure of the material and further treatment as described in Example 1, a cyan image which shows a very low side absorption in the green and the blue is obtained.

EXAMPLE 3 10 parts of N-(3-carboxy-4-cetylsulphonylphenyl)- l-hydroxy-Z-naphthoic acid amide are Wetted with 30 parts of ethanol and dissolved in parts of alkali N and 145 parts of water. The color coupler solution is incorporated into the emulsion according to Example 1. The emulsion is neutralized by 7.5 parts of acetic acid N/2 per 100 parts of color coupler solution. The exposure as well as the development are carried out as described in Example 1, taking into account, however, that in the color developing bath the N,N-diethyl-pphenylene diamine hydrochloride is replaced by 4-amino- N ethyl N-(B-methyl-sulphonamidoethyl)m-tolui-dinesesquisulphate monohydrate. A cyan image with low side absorptions is obtained.

EXAMPLE 4 200 parts of a solution 5% of N-(6'-cetylsulphonylphenyl)-1-hydroxy-2-naphthoic acid amide-3'-sodium sulphonate dissolved in a mixture of ethanol and water (3:7) and 260 parts of water are added to 500 parts of v18 to 20 C. and treated for 5 minutes 6 a red-sensitized silver io-do-bromide-emulsion (2% iodide). This emulsion is coated on a photographic support. After exposure, color development and further treatment according to Example 1, an intense cyan image with low side-absorptions in the green is obtained.

EXAMPLE 5 To 450 g. of silver 'bromo-io-dide emulsion and 45 cm. of water are added 20 cm? of a solution 0.1% of the sensitizer for red [2-(3-methyl-5-phenyl-2,3-benzthiazoline)] [2'-(1 methylnaphtho[1,2]thiazole)H3- ethyl trimethinecyanine-methylsulphate. To this emulsion are added 70 cm. of an alkaline solution 10% (0.5% sodium hydroxide) of the color coupler for cyan N 6-cetylsulphonylphenyl) l-hydroxy-Z-naphthoic acid amide-3'-sodium sulphonate together with 25 cm. of an alkaline solution 20% (0.6% sodium hydroxide) of 1,2- dimethyll-amino-S-nonyl pyrazolone-3 hydrochloride. The whole mixture is neutralized by 12 cm. of acetic acid N. This product is as usual chrome hardened Whereafter a stabilizing agent together with a wetting agent are added. This emulsion is coated in ratio of g./sq. m. on a photographic support. After exposure, the photographic material thus obtained is treated according to Example 1. Besides a negative cyan image a positive magenta image is formed which compensates completely the unwanted absorptions in the green and to a great extent in the blue.

EXAMPLE 6 To a red-sensitized silver bromo-iodide emulsion containing about /3 mol of silver halide per kg. of emulsion are added per mol of silver halide 240 cm. of a solution 10% of N-(6-cetylsulphonylphenyl)-l-hydroxy-2- naphthoic acid amide-3-sodium sulphonate in alcohol with a little sodium hydroxide and next cm. of a solution 10% of 1,2 dimethyl 4 amino-S-tridecylpyrazolone-S in methylcellosolve with a little sodium hydroxide. After acidification to pH 6 and after addition of the usual additives such as hardeners, wetting agents and stabilizers, the emulsion obtained is coated on a suitable support and dried. After exposure through a red filter (Gevafilter R 678 marketed by Gevaert Photo-Producten N.V., Mortsel, Belgium) and a grey wedge with a constant 0.15, the photographic material composed in this way is developed for 9 minutes at 20 C. in a color developing bath with the following composition:

This material is rinsed for 30 minutes at 18 to 20 C. and fixed for 5 minutes at 20 C. in a fixing bath of the following composition:

G. Sodium thiosulphate 200 Sodium bisulphite 25 Potassium alum 20 Sodium biacetate 20 Boric acid 7.5

Water to 1000 cm. (pH=4.0).

Next, the material is rinsed again for 10 minutes at in a bleaching bath of the following composition:

Water to 1000 cm. '(pH=8.6).

Rinsing is continued for another 10 minutes at 18 to 20 C. and then the material is fixed again for minutes at 20 C. in a bath of the following composition:

G. Sodium thiosulphate 130 Borax 2 0- Magnesium sulphate 50 Water to 1000 cm. (pH=8. 9).

EXAMPLE 7 To a red-sensitized silver bromo-iodide emulsion containing about Va mol of silver halide per kg. of emulsion are added per mol of silver halide 240 cm. of a solution of N-(6'-cetylsulphonylphenyl)-1-hydroxy-2- naphthoic acid amide-3'-sodium sulphonate in alcohol with a little sodium hydroxide and next 120 cm. of a solution 10% in methylcellosolve of the methylester of 1 methyl 2v (psuccinylamidophenyl).-4-amino-5- pentadecylpyrazolone-3 with a little sodium hydroxide. After further treatment as in Example 6-, a. cyan image is obtained wherein the disturbing influence of the side absorptions is reduced by the formed magenta masking image with opposite gradation to the cyan image.

' EXAMPLE 8 To a red-sensitized silver bromo-iodide emulsion containing about /3 mol of silver halide per kg. of emulsion areadded. per mol of silver halide 240 cm. of a solution 10% of N-(6-cetylsulphonylphenyl)-1-hydroxy-2 naphthoic acid amide-3-sodium sulphonate in alcohol with a little sodium hydroxide and next 120 cm. of a solution 10% in methyl cellosolveof 1-methyl-2-(2'- chloro-S'-carbomethoxyphenyl 4 amino-S-pentadecylpyrazolone-3 with a little sodium hydroxide. After further treatment as in Example 6 a cyan image is obtained wherein the disturbing influence of the side-absorption is reduced by the formed magenta mask image with opposite gradation tothe cyan image.

EXAMPLE 9 Before coating a red-sensitized silver halide emulsion containing /3 mol of silver halide/kg. emulsion 240 cm. of an alcoholic sodium hydroxide solution 10% of N-(6'- cetylsulphonylphenyl)--1-hydroxy-4-chloro 2i naphthoic acid amide-3'-sodi-um sulphonate are added to this emulsion per mol of 'silverhalide and next 120. 'cm. of. a solution 10%- of l,Z-dimethyl-4-amino-S-tridecyl-pyrazolone-3-in methyl cellosolve witha little sodium hydroxide.

After acidification with acetic acid to a pH 6 and after the ordinary addition of hardening agents and stabilizers, this emulsionis coated on a. support provided with an anti-halation layer. To this emulsion layer is successive- 1y coated a thin gelatin layer, a green light-sensitized silver bromo-iodide emulsion layer with a color coupler for magenta, a yellow filter layer consisting of gelatin With dispersed colloidal silver, a blue sensitive silver bromcyiodide silver layer with color coupler for yellow, andfinally an anti-stress layer. After exposure and further finishing such as in Example 6, a dyestufi image is obtained the red light-sensitized emulsion layer of which contains a cyan dyestuif image the unfavorable side-absorptions of which are masked by a magenta mask image with opposite gradation.

The accompanying absorption curves give a comparative image of theabsorption spectra of compounds prepared before and thoseprepared according to the present invention.

Curve-1+ Absorption curve of the developed color coupler prepared according' to Germanpatent specifica- 8 tion 930,795, page 2, lines 34-41 but C H is substituted for C18H37.

Curve Ii: Absorption curve of the developed color coupler prepared according to the German specification 1,036,053, Example 1.

Curve III: Absorption curve of the developed color coupler according to preparation III in the foregoing description The developer for the three cases is N,N-diethyl-pphenylenediarnine.

As appears from the above, the course of curves I and II corresponds somewhat whereas curve III points to ahigher transparency in the green of the spectrum.

We claim:

1. Process for obtaining a colored photographic image in a reducible silver halide emulsion layer, comprising exposing said layer and developing same with a primary aromatic amino developing agent in the presence of a color coupler for cyan, selected from the group consisting of and C O-NH SO -R wherein X represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a sulphonic acid group and a sulphonate group;

Y represents a member selectedfrom the group consisting of a carboxyl group, a sulphonic acid group and a sulphonate group.

R represents an aliphatic radical comprising a linear chain of at least 5 and at most 20 Oatorns and rendering said coupler resistant to diffusion;

2. A multilayer photographic color film comprising a plurality of superposed differentiallylight-sensitive silver halide emulsion layers containingin the red'sensitive silver halide emulsion layer a color coupler for cyan selected from the-group consisting of on s ope oo-NH and o'o'-Nn- I l x Y aoraaae wherein X represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a sulphonic acid group and a sulphonate group;

Y represents a member selected from the group consisting of a carboxyl group, a sulphonic acid group and a sulphonate group;

R represents an aliphatic radical comprising a linear chain of at least and at most 20 C-atoms and rendering said coupler resistant to diffusion.

3. Photographic element having superposed silver halide emulsion layers sensitive to different regions of the visible spectrum, at least one of said layers containing a color coupler for color development selected from the group consisting of:

on Sim-R and wherein X represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a sulphonic acid group and a sulphonate group;

Y represents a member selected from the group consisting of a carboxyl group, a sulphonic acid group and a sulphonate group;

R represents an aliphatic radical comprising a linear chain of at least 5 and at most 20 C-atoms and rendering said coupler resistant to diffusion,

which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a cyan dye image which absorbs a major proportion of light in the red region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, and a 4-aminopyraZolo-ne-3 derivative with the following general formula less than 20 carbon atoms rendering said derivative resistant to diffusion,

said color coupler being also reactive with the oxidation product of said 4-amino-pyrazolone-3 derivative to form a secondary dye image having a graduation opposite to that of said cyan dye image, and absorbing light in at least one of said said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region.

4. The photographic element of claim 3 wherein said color coupler is N-(4-cetyl-sulphonylphenyl) 1 hydroxy-Z-naphthoic acid amide-3-Sodium sulphonate.

5. The photographic element of claim 3 wherein said color coupler is N-(6-cetylsulphonylphenyl)1-hydroxy- Z-naphthoie acid amide-4,3-disodium sulphonate.

6. The photographic element of claim 3 wherein said color coupler is N-(6-cetylsulphonylphenyl)l-hydroxy- Z-naphthoic acid amide-3-sodium sulphonate.

7. The photographic element of claim 3 wherein said pyrazolone derivative is l,2-dimethyl-1,4-amino-5-nonylpyrazolone-3hydrochloride.

8. The photographic element of claim 3 wherein said pyrazolone derivative is 1,2-dimethyl-4-amino-5-tridecy1- pyrazolone-3.

9. The photographic element of claim 3 wherein said pyrazolone derivative is 1-methyl-2-(p-succinylamidophenyl) -4-amino-5-pentadecylpyrazolone-3.

10. The photographic element of claim 3 wherein said pyrazolone derivative is l-methyl-Z-(2-chloro-5-carbomethoxyphenyl)-4-amino-5-pentadecylpyrazolone-3.

No references cited. 

1. PROCESS FOR OBTAINING A COLORED PHOTOGRAPHIC IMAGE IN A REDUCIBLE SILVER HALIDE EMULSION LAYER, COMPRISING EXPOSING SAID LAYER AND DEVELOPING SAME WITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF A COLOR COUPLER FOR CYAN, SELECTED FROM THE GROUP CONSISTING OF 